Method for producing alkylene oxide condensation products



Feb. 19, 1952 R A WILSON 2,586,767

METHOD FOR PRODUCING ALKYLENE OXIDE CONDENSATION PRODUCTS Filed Jan. 31, 1948 ROBERT A. WILSON INVENTOR.

ATTORNEY Patented Feb. 19, 1952 mrrnon ron raonUcmG ALKYLENE oxma CONDENSATION raonucrs Robert A. Wilson, Anniston, Aia., assignor to Monsanto Chemical Company, St. Louis, Mo.,

a corporation of Delaware Application January 31, 1948, Serial No. 5,805

12 Claims. (Cl. 260-975) The present invention relates to detergents, surface-active materials and assistants for use in textile and related industries and to a novel method of producing same.

An object of the invention is to provide an economically and commercially feasible method of producing condensation products of alkylene oxides and water-insoluble, monomeric, organic compounds selected from the group consisting of hydroxy, carboxy, amino and mercapto compounds containing at least 6 carbon atoms and one reactive hydrogen atom.

An additional object is to provide a method of producing condensation products of the above type in which the reaction conditions and quality of product may be readily controlled.

Another object is to provide a method of producing the above products in which substantial reduction in power requirements is obtained over those of prior art methods involving the use of an agitated type reactor.

Another object is to provide a method of producing the above products in which the reaction conditions and products are readily reproducible and predictable and therefore translation from a plant of a given productive capacity to one of substantially difierent capacity can be readily made without resorting to extensive experimentation.

A further object is to provide a method of producing the above products in which the'reaction proceeds at a substantially higher rate than that of prior are methods operating at comparable pressures.

A still further object is to provide a method of producing the above compounds which is considerably safer to operate than the methods of the prior art. I

Other objects and advantages will be apparent to those skilled in the art as the description of the invention proceeds.

It is known in the art that numerous valuable products are obtainable by reacting ethylene oxide with water-insoluble organic compounds containing at least one reactive hydrogen atom, i. 'e. at least one hydroxy, carboxy, mercapto or amino group.

For example, in accordance with application Serial Number 637,079, filed December 22, 1945, now abandoned, in thename 01' Milton Kosmin, if ethylene oxide is reacted with abietic acid or products containing same, water-soluble, nonresinous products are obtained. These products are valuable for purposes such as in textile treating compositions'where they may be used as detergents or softening agents. They also may be control of electrolytic metal deposits and in cosmetics or ointments, where by virtue of their water-solubility, they may be readily removed by washing in water.

Also, in accordance with application Serial Number 637,096, filed December 22, 1945, now abandoned, in the name of Jay C. Harris and Milton Kosmin, it abietic acid or products containing same, such as rosin, rosin oil or tall oil are reacted with ethylene oxide in amount such that at least 0.5 part. but less than 2.3 parts. of ethylene oxide per part of abietic acid are condensed and the condensation product thus obtained combined with alkali metal phosphates, detergent compositions having improved washing effects are obtained. Thus these compositions are particularly adapted for use in automatic washing machines, especially in the closed type of washer because of the almost total absence of suds. This non-sudsing action is highly desirable as it has been found that the use of the ordinary sudsing type of detergent in such machines results in a' somewhat decreased efficiency due to the mechanical blanketing oi the drop of the clothes by the excess amount of suds. Furthermore, due to the markedly reduced tendency to foam of the above detergents. it is possible to increase the speed of the agitator or spinner resulting in an increase in the efllciency of extraction of the wash water.

Moreover, in accordance with application Serial Number 718,133, filed December 23, 1946, in the name of Milton Kosmin, if branched-chain mercaptans having from 6 to 18 carbon atoms per a mole are reacted with from one to forty moles of ethylene oxide or propylene oxide, surface active agents of particular effectiveness in hard water are obtained. Of these, the condensation products obtained from mercaptans and ethylene oxide are particularly powerful non-ionic wetting agents and by varying the ethylene oxidemercaptan ratio the wetting power and softening effects of these products on fabrics may be modified. Further, these products being nonionic are not afiected by metallic ions and possess great stability in acid and basic solutions. These surface active agents may also be formulated as commercial compositions by the addition of various adjunct and builder materials and detergents as is common in the art.

Furthermore, in'accordance with application Serial Number 576,374, filed February 5, 1945, now abandoned, in the name of Earl W. Gluesenkamp and Jay C. Harris, 11' irom 10 to 30 moles oi ethylene oxide are reacted with one mole of an N-methylol amide having the general structure:

R.CONH.CH2OH wherein R is an aliphatic hydrocarbon radicle of from 11 to 27 carbon atoms, valuable products 4 1 mechanical mixing of the liquid reaction phase with the gaseous ethylene oxide. This method constituted a substantial improvement over those hereinbefore described, but it has a number of are obtained which are suitable for the textile and related industries. These condensation products vary from viscous liquids to waxy or crystalline solids at room temperature, depending upon the number of carbon atoms and degree of unsaturation in the acyl group and the number of moles of ethylene oxide with which the N-methylol amides have been reacted. They are of particular importance in the field of synthetic detergents in that they are non-foaming detergents, i. e., they serve as very eflicient detergents and at the same time produce little, if any,, suds, which property is very desirable in detersive agents that are to be used in many types of washing machines.

For numerous other valuable products which may be prepared by condensing ethylene oxide with compounds of the above type, amines, alcohols and many other water-insoluble organic compounds containing at least one reactive hydrogen atom, reference is made to Patent 1,970,578 to Conrad Schoeller et al.

Heretoiore, a number of methods of preparing the above condensation products have been attempted, but they have all proved to be commercially unattractive from the standpoint of operation, capital cost and large scale production.

For-example, in accordance with one method, the reaction was carried out by bubbling ethylene oxide into tall oil, but it was found that the absorption rate was relatively slow and consequent- 1y unduly large and expensive equipment was required for large volume production. Moreover, this method had the disadvantage of presenting an explosion hazard as mechanical failure resulting in an increase in pressure in the reactor or a a decrease in pressure in the ethylene oxide feed tank would cause the reaction mixture to be forced into the ethylene oxide feed tank where an explosion would be likely to occur in view of the highly exothermic nature of the ethylene oxide-tall oil reaction.

In another method, the reaction was executed in a Calandria type reactor which involved the use of a heat exchanger immersed in tall oil to absorb the heat of reaction and also an agitator for circulating the liquid through the heat exchanger into contact with the gas phase. However, since no improvement in ethylene oxide absorption and reaction rates was obtained and since excessively large and expensive equipment was also required for large scale production, this method was abandoned as being commercially unattractive.

A further method which proved unsuccessful consisted in introducing ethylene oxide into the suction side ofa centrifugal pump which circulated a stream of tall oil in a cyclic system including a reactor. However, the absorption or reaction of ethylene oxide with tall oil was relatively slow and as this method also presented the same type of explosion problem as that described above, it was discarded as being hazardous and impractical.

A still further method comprised reacting ethylene oxide with tall oil in an autoclave provided with an external heat exchanging medium for heating and cooling the reaction mixture, and also a vertically mounted agitator for violent disadvantages which render it. commercially unattractive.

One disadvantage of the above method is that as the reaction proceeds, the volume of the reaction mixture increases and in agitating the charge, the level of the liquid reaction phase rises above the agitator paddles and this calls for an increase in their number in order to compensate for the resulting loss of agitation. Thus, in order to obtain agitation of sufficient intensity to eifect adequate contact between the gas and liquid phases, a substantial number of agitator paddles would have to be employed and this excessively increases the power requirements. Another disadvantage is that there is danger of leakage of ethylene oxide through the stufilng box around the agitator shaft which renders the operation hazardous due to the explosive nature ofethylene oxide. A further disadvantage is that the reaction conditions are not readily reproducible and predictable and consequently translation from a plant of a given productive capacity to one of a different capacity cannot be made readily without resorting to extensive experimentation. Finally, the ethylene oxide absorption rate is relatively slow and is therefore unsatisfactory for large scale production and while faster reaction rates probably could be achieved by using a relatively large number of agitator paddles. it would not be economically and commercially feasible to do so as the power reqirements would be excessive.

I have developed a novel method of carrying out the above condensation reactions at a surprisingly rapid rate, which has none of the objectionable features mentioned above.

In accordance with this method, an organic compound containing at least one reactive hydrogen atom is sprayed in a finely divided state into an absorption zone (which may or may not contain an inert gas) which is continuously supplied with ethylene oxide at a rate adapted to maintain the total pressure therein substantially constant. The finely divided droplets of the above organic compound avidly absorb the ethylene oxide vapor and then rapidly react therewith with the result that a relatively large amount of exothermic heat is developed which must be absorbed. This is accomplished in any manner well known to those skilled in the art, but it is preferred to withdraw the reaction products from the reactor, cool and then recycle them to the absorption zone for further absorption and reaction with ethylene oxide. This cycle of operations is repeated at a very rapid rate until a predetermined number of ethenoxy groups have been introduced into the organic compounds.

It is essential to safe operation of the above method that an inert atmosphere be employed in the absorption and reaction steps and for this purpose, nitrogen, methane, butane or any other suitable inert gas may be used. In carrying out this embodiment of the invention, an inert gas is charged to the reactor in an amount suflicient to provide a pressure therein of about one atmosphere and then ethylene oxide is added until its partial pressure is built up to about 6 to about 55 lbs. per square inch. Upon completing these operations, the tall 011 is circulated as above at a temperature within the range of C. to 200 C. until from 1 to 50 and preferably from 6 to 20 8 moles of ethylene oxide have been condensed with each mole of organic compound.

For a more complete understanding of the pres ent invention reference is made to the accompanying drawing which shows in conventional side elevation one particular embodiment of the invention. It should be emphasized, however, that modifications and variations in the equipment apparent to those skilled in the art may be made as desired without departing from the broad scope of the invention.

Referring to the drawing, reference character i represents a line leading from a liquid ethylene oxide storage tank (not shown) to an ethylene oxide feed tank 2 which is provided with an inlet 3 for introducing nitrogen under pressure by line t and an outlet 5 connected to line 6 for venting and reducing the feed tank pressure below that of the storage tank pressure, thus permitting the flow ofethylene oxide from storage to the feed tank. When desired, ethylene oxide is forced out of the feed tank by nitrogen pressure and conveyed by line I, valve 8, line 9 and inlet into spray reactor ii at a rate such that the total pressure therein is maintained substantially constant, the rate of feed being regulated by pressure controller i2 which opens or closes valve 8 in response to variation in pressure in the reactor.

Reference character it represents the line for feeding tall oil to the tall oil feed tank i I which is provided with a steam'coil i for heating and drying the tall oil. The dried tall oil is fed from this tank by line [6, valve i1, line It, pump it, line 20, valve 2! and lines 22 and 23 into the spray reactor by way of inlet 24. A spray 25 is attached to the end of line 23 for atomizing the tall oil (or reaction mixture).

The reactor ii is provided with a vent line 28 for venting nitrogen and an external high pressure steam coil 26 for drying tall oil or heatin it up to temperature prior to circulating and reacting same with ethylene oxide.

The products of the ethylene oxide-tall oil reaction are discharged from the reactor i I by outlet 2! into line I8 and are forced by pump i9 through line 20 to a three way valve 2i which controls the amount of flow to lines 22 and 28 depending upon the temperature of the reaction mixture.

The operation of valve 2| is regulated by temperature controller 29 which is responsive to the temperature of the reaction mixture within the reactor. If the reaction temperature exceeds a predetermined value, the temperature controller actuates valve 2i in such a manner that the flow through line 22 is decreased and the flow through line 28 to the heat exchanger 30 is increased. After the flow through line 28 is cooled in the heat exchanger, it is mixed in line 23 with the flow from line 22 and the resulting mixture returned to the reactor. On the other hand, if the temperature of the reaction mixture is not excessive or is too low, then the controller decreases the flow through line 28 to the heat exchanger and increases, the flow through line 22, the two streams being ultimately combined in line 23 and then recycled to the reactor.

After the desired quantity of ethylene oxide has been reacted with tall oil, the product is pumped to storage by pump I! through line 20, line 3i, valve 32 and line 33.

Typical operating conditions which may be employed in carrying out the method illustrated in the drawing are substantially as follows:

Tall oil is charged to the feed tank It where v a it is mixed with a suitable catalyst such as potassium hydroxide and dried by heating to a temperature of 150 C. to 160 C. for 30 to minutes. The dried tall oil is then pumped to reactor il in the manner described above.

After closing valve il, the circulation of the dried tall 011 is initiated by operating pump it and with the tall 011 circulating through the reactor, the ethylene oxide feed tank 2 is charged by reducing the feed tank pressure below that of the storage tank pressure. This is accomplished by venting the feed tank through line 8 into reactor ii wherein the ethylene oxide vapor is absorbed from the nitrogen by the circulating tall oil. The nitrogen is vented to the atmosphere through line 28 and, in doing this, care is exercised to leave sufllcient nitrogen pressure, 1. e., about 14.7 lbs./in.=, in the reactor to form a safe (non-explosive) mixture with ethylene oxide.

After charging the ethylene oxide feed tank 2 and adjusting the initial nitrogen pressure in the reactor ii, the pressure in the ethylene oxide feed tank 2 is increased sufficiently to cause the flow of liquid ethylene oxide through line I, valve 8 and line 8 into the reactor where it is immediately vaporized. The circulating tall oil absorbs and reacts with the vaporized ethylene oxide and as these operations proceed, pressure controller I: actuates valve 8 to maintain a constant total pressure in the reactor by regulating the flow of ethylene oxide thereto.

The reaction of ethylene oxide with tall 011 is highly exothermic and the liquid mass in the reactor is preferably maintained at a predetermined temperature in the range of 150 C. to

175 C. by means of temperature controller 23 which actuates valve 2i to cause all or part of the flow of liquid from the bottom of the reactor to be directed through the water cooled heat exchanger 30 as required.

The circulation of the tall oil through the reactor is continued until to 160 lbs. or any other desired amount of ethylene oxide has been absorbed and reacted and at the completion of the reaction, the resulting product is pumped to storage by pump i9 through line 2ll, line 3!, valve 32 and line 33.

The following examples will serve to illustrate several embodiments of the invention involving the use of difierent operating conditions.

Example I A charge of 100 lbs. of dry tall oil containing 2% by weight of KOH was introduced at a temperature of about C. into the reactor. Then nitrogen and ethylene oxide were charged in amounts sufficient to produce partial pressures in the reactor of 14.7 and 27 lbs. per square inch respectively.

Upon completing the above operations, the tall oil was repeatedly circulated and sprayed into the reaction at a temperature of from 164 C. to 171 C. and as the ethylene oxide vapor was rapidly absorbed and reacted. it was replenished by the ethylene oxide feed tank which supplied this material at a rate such that the total pressure in the reactor was maintained substantially constant. The circulation of the tall oil through The reactor was charged with 100 lbs. of dry tall oil containing 4% by weight or potassium hydroxide and then nitrogen and ethylene oxide vapor were successively introduced inamounts adapted to produce partial pressures in the reactor of 14.7 and 27 lbs. per square inch respectively. v

The tall oil was circulated and sprayed at a temperature of about 153" c. to 165 0. into the Example III 100 lbs. of tall oil containing 2.4% by weight of potassium hydroxide was dried in the tall oil feed tank by heating it to a temperature of about 150 C. for about 30 to 60 minutes, whereupon it was charged to the spray reactor.

After introducing butane and ethylene oxide vapor into the reactor in amounts providing par+ tial pressures of about 14.7 lbs. and 55 lbs. per square inch respectively, the tall oil was circulated through the reactor for about 48 minutes at a temperature of from about160 C. to about 180 C. and during this time ethylene oxide was introduced at a rate adapted to maintain the total pressure in the reactor substantially constant. The resulting reaction product contained tall oil and ethylene oxide combined in a ratio of 1 to 1.4 parts by weight respectively.

Example IV A charge of 100 lbs. of tertiary dodecyl mercaptan containing 1% by weight of potassium hydroxide was supplied to the reactor and then nitrogen and ethylene oxide were added successively until partial pressures in the reactor of 14.7 and 2-3 lbs. per square inch respectively were obtained.

The above mercaptan was then circulated and sprayed at a temperature of about 52 C. to 61 C into the reactor for a period of 1 hour and during this time, ethylene oxide was supplied from the feed tank as rapidly as it was being absorbed and reacted with the mercaptan.

An additional 1% by weight of potassium hydroxide was introduced and after raising the temperature to 115 C. to 142 C. and increasing the ethylene oxide partial pressure therein to about -15 lbs. per square inch, the circulation of the charge through the reactor was continued for 3 hoiirs and minutes longer. The resulting product was an amber colored oily liquid which contained the above mercaptan and ethylene oxide combined in a weight ratio of 1 partto' 2.0 parts by weight respectively.

The products of Examples I-IV were evaluated for detergency by the standard Launderometer procedure described by Jay C. Harris in "Soap and Sanitary Chemicals" for August and September, 1943. The hard" water employed had a hardness of 300 p. p. m. and the detergents were used in a concentration of 0.2% by weight. However, instead of reporting the results as per cent of soil removed, as described by Harris, the effectiveness of the detergent is compared with that of Gardinol WA (sodium lorol sulfate), the value of which is taken as 100%. Accordingly, the detergency results herein reported are referred to as "relative detergency. Using the above procedure as a standard. the following results were obtained:

Relative detergency 300 p p. m. Gardinol basis, per cent Product of Example I 121 Product of Example 11 Product of Example III 91 Product of Example IV 108 These results show a relative detergency of from 91% to 121% on a Gardinol basis, thus indicating that high quality products are obtained by the method of the instant invention.

The various conditions of operation will now be discussed in greater detail.

In producing condensation products in accordance with the present invention, the reaction is carried out at a temperature of about 125 C. to

about 200 C. and within this range a temperature of C. to C. is preferred. However,

it should be clearly understood that lower or higher temperatures may be employed if desired provided temperatures resulting in substantial decomposition of the product are avoided.

The water-insoluble monomeric organic compounds containing at least one reactive hydrogen atom are preferably reacted with ethylene oxide in the presence of condensation catalysts. Suitable materials for this purpose are bleaching earths or active charcoal, strongly acid substances such as sulfuric or phosphoric acids, or sodium or potassium bisulfates, or strongly alkaline agents such as potassium hydroxide, sodium hydroxide or alkali metal alcoholates. In general, the most satisfactory catalyst varies with the reaction involved and in view of the broad scope of the instant invention, no attempt will be made to specify the catalyst or quantity of catalyst required for each reaction. However, it is desired to point out that in the production of the preferred products, l. e., the condensation products of ethylene oxide with abietic acid, tall oil or branched-chain mercaptans, potassium hydroxide is the preferred catalyst and it is employed in an amount varying from about 1% to about 5% by weight of the initial material and within this range about 4% by weight is preferred.

The above condensation reactions proceed at a surprisingly rapid rate which is made possible by the absorption technique employed. In accordance therewith, the above organic compounds are sprayed or otherwise introduced in a finely divided state into an absorption zone which is continuously supplied with ethylene oxide at a rate designed to maintain the total pressure therein substantially constant. The finely divided particles absorb and rapidly react with ethylene oxide and the exothermic heat developed is absorbed in any suitable manner at a rate suflicient to maintain the liquid product at a temperature of about 125 C. to about 200 C. and preferably at a temperature within the range of from 150 C. to 175 C. The preferred method of accomplishing this is illustrated in the accompanying drawing, but the invention is not restricted thereto.

After cooling the reaction products, they are recycled to the absorption zone where they absorb and react with additional quantities of ethylene oxide. These operations are repeated until the desired number of ethenoxy groups have been introduced into the above organic compounds. This number may vary from 1 to 50 ethenoxy groups per active hydrogen group or more specifically from 1 to 50 and preferably from 6 to 20 ethenoxy groups per molecular proportion of organic compound. For a more detailed statement regarding the proportions in which the above reactants may be combined to yield products of varying properties, reference is made'to the copending applications and patent referred to earlier herein, which applications and patent are incorporated by reference in the present specification.

As indicated above, in order to insure safe operation, the absorption and reaction steps are executed in the presence of nitrogen, methane, butane or another inert gas. The amount of inert gas employed may vary within wide limits provided the ethylene oxide partial pressure is adjusted so that the explosive limits of the gas mixture are not exceeded. Thus, in the specific examples, the use of an inert gas under atmos pheric pressure is merely illustrative of one convenient operating pressure and it is to be understood that the invention is not restricted thereto.

The ethylene oxide partial pressure may also fluctuate widely and while from 6 to 55 lbs. per square inch is a convenient operating pressure range, higher or lower pressures may be used if desired. Stated broadly, the ethylene oxide partial pressure should be controlled so that the explosive limits of the pure gas or mixtures thereof with inert gases are not exceeded. Expressed in terms of reaction temperature, the ethylene oxide partial pressure is so adjusted as to prevent the reaction from proceeding at a rate sufficient to liberate enough heat to cause the temperature of the liquid mass to exceed 200 C., and preferably 175 C.

It is desired to point out that while the reaction of ethylene oxide with an organic compound containing at least one active hydrogen atom takes place to some extent throughout the entire cycle of the latter, the major part of the reaction apparently occurs after the droplets containing ethylene oxide have coalesced in the bottom of the reactor. However, by lengthening the absorption zone, adjusting the ethylene oxide partial pressure, properly adjusting the temperature therein and controlling the rate of circulation, the reaction can be made to take place while the above organic compound is in the atomized state and therefore the present invention contemplates both of the above methods of operation.

The present invention resides in the introduction of organic compounds having at least one reactive hydrogen atom in a highly comminuted state into an atmosphere of ethylene oxide whereby the latter is absorbed and reacted at an exceedingly rapid rate.

plished by means of one or more sprays, but if desired, agitators of various types may be used in combination therewith to further increase the ethylene oxide absorption and reaction rates. Moreover, other atomizing devices known to those skilled in the art may be used to supplement or replace the above sprays and where such devices are adopted to serve the latter purpose, the product is recycled by way of a heat exchanger merely for the purpose of controlling the temperature of the reaction. If, however, the '5.

means for absorbing the heat of reaction is located in the reaction zone, then recycling of the product is unnecessary.

Although the foregoing description has been limited to ethylene oxide, it is to be clearly understood that it is also within the scope of the present invention to use propylene oxide. butylene oxide and other alkylene oxides boiling below 200 C.

A reactive hydrogen atom as used in the instant specification and claims is a hydrogen atoms connected to a nitrogen, oxygen or a sulfur atom in an organic compound such as amines, amides, alcohols, phenols, carboxylic acids, mercaptans, etc. Numerous illustrative examples of organic compounds having active hydrogen atoms are found in Patent 1,970,578 to Conrad Schoeller et al. and in application Ser. Nos. 637,079, 637,096, and 576,374 hereinbefore cited.

The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. and it is therefore desired that the present embodiments be considered in all respects as illustrative and not restrictive, reference being had to the appended claims rather than to the foregoing description to indicate the scope of the invention.

I claim:

1. The method of producing condensation products which comprises continuously introducing an unsubstituted alkylene oxide which boils The comminution of the above organic compound is preferably accombelow 200 C. into a reaction zone at such a rate that the pressure in said zone is maintained substantially constant, spraying in a finely divided liquid form into said zone an organic compound containing at least one reactive hydrogen atom and at least six carbon atoms which then reacts with a portion of said alkylene oxide, cooling and continuously recycling and spraying the resulting products into said zone for further reaction until a predetermined number of alkylene oxide groups have been introduced into said compound, said organic compound being selected from the group consisting of hydroxyl, carboxyl, amino and mercapto compounds, and said cooling being sufficient to maintain said reaction at a temperature at which substantial decomposition of said reaction product is avoided.

2. The method of producing condensation products which comprises continuously introducing an unsubstituted alkylene oxide boiling below 200 C. into a reaction zone containing an inert gas, spraying in a finely divided liquid form into said zone an organic compound containing at least one reactive hydrogen atom and at least six carbon atoms which then reacts with a portion of said alkylene oxide, cooling and continuously recycling and spraying the resulting products into said zone until from 1 to 50 alkylene oxide groups have been introduced into said organic compound, and said cooling being sufiicient to maintain said reaction at a temperature at which substantial decomposition of said reaction product is avoided.

3. The method of producing condensation products which comprises continuously introducing an unsubstituted alkylene oxide containing from 2 to 4 carbon atoms into a reaction zone, containing an inert gas, spraying in a finely divided liquid form into said zone an organic material selected from the group consisting of abietic acid, tall oil and a branched chain alkyl mercapt'an having 6 to 18 carbon atoms in the molecule which then reacts with a portion of said alkylene oxide, cooling the resulting reaction products outside said reaction zone and continuously recycling and spraying same into said zone until from 6 to 50 alkylene oxide groups have been introduced into said organic material and, said cooling being sufiicient to maintain said reaction at a temperl l ature at which substantial decomposition 01' said reaction product is avoided.

4. The method defined in claim 3, wherein the alkylene oxide is ethylene oxide and the inert gas is selected from the group consisting of nitrogen, methane and butane.

5. The method defined in claim 3 wherein the alkylene oxide is ethylene oxide, the inert gas is methane and the pressure of the mixture of said gases in the reaction zone is from about 20 lbs. to about 70 lbs. per square inch, and the total pressure therein is maintained substantially constant.

6. The method defined in claim 5 wherein the partial pressure of the ethylene oxide is about 6 to about 55 lbs. per square inch.

7. The method of producing condensation products which comprises continuously introducing ethylene oxide into a reaction zone, spraying into said zone finely divided tall oil which reacts with a portion of said ethylene oxide, coolin and continuously recycling and spraying the resulting products into said zone until 1.6 parts by weight of ethylene oxide have reacted with 1 part by weight of said tall oil, said reaction being carried out at a temperature of about 150 C. to about 175 C. and said cooling being sufiicient to maintain said reaction temperature.

8. The method of producing condensation products which comprises continuously introducing ethylene oxide into a reaction zone, spraying into said zone finely divided tall oil which reacts with a portion of said ethylene oxide, cooling and continuously recycling and sprayingthe resulting products into said zone until 1.4 parts by weight of ethylene oxide have reacted with 1 part by weight of said tall oil, said reaction being carried out at a temperature of about 158 C. to about 175 C. and said cooling being sufiicient to maintain said reaction temperature.

9. The method of producing condensation products which comprises continuously introducing ethylene oxide into a reaction zone, spraying into said zone finely divided tall oil which reacts with a portion of said ethylene oxide, cooling and continuously recycling and spraying the resulting products into said zone until 1.4 parts by weight of ethylene oxide have reacted with 1 part by weight of said tall oil, said reaction being carried out at a temperature of about 160 C. to about 180 C. and said cooling being suflicient to maintain said reaction temperature.

10. The method of producing condensation products which comprises continuously introducing ethylene oxide into a reaction zone, spraying into said zone finely divided tertiary dodecyl mercaptan which reacts with a portion of said ethylene oxide, cooling and continuously recycling and spraying the resulting products into said zone until 2.0 parts by weight of ethylene oxide have reacted with 1 part by weight of said mercaptan,

said reaction being carried out at a temperature perature.

11. The method of producing condensation products which comprises continuously introducing ethylene oxide into a reac ion zone containing an inert gas selected from ;he group consisting of nitrogen, methane and butane, spraying in a finely divided liquid form into said zone an organic material selected from the group consisting 01' abietie acid, tall oil and a branched chain alkyi mercaptan having 6 to 18 carbon atoms in the molecule which then reacts with a portion of said ethylene oxide, cooling the resulting reaction products outside said reactio'n zone and continuously recycling and spraying same into said zone until from 6 to 50 ethenoxy groups have been introduced into said organic material, said reaction being effected at a temperature within the range of about 125 C to about 200 C. and said cooling being sufiicient to maintain said reaction temperature.

12. The method of producing condensation products which comprises continuously introducing ethylene oxide into a reaction zone containing an inert gas selected from the group consisting of nitrogen, methane, and butane, spraying in a finely divided liquid form into said zone an organic material selected from the group consisting of abietic acid, tall oil and a branched chain alkyl mercaptan having 6 to 18 carbon atoms in the molecule which then reacts with a portion of said ethylene oxide, cooling the resulting reaction products outside said reaction zone and continuously recycling and spraying same into said zone until from 6 to ethenoxy groups have been introduced into said organic material, said reaction being efiected at a temperature within the range of about C. to about C. and said cooling being suilicient to maintain said reaction temperature.

ROBERT A. WILSON.

REFERENCES CITED The following references are of record in th file of this patent:

UNITED STATES PATENTS Number Name Date 1,005,882 Rinman Oct. 17, 1911 1,417,006 Howard May 23, 1922 1,976,677 Wittwer Oct. 9, 1934 2,194,429 Krzikalla Mar. 19, 1940 2,205,021 Schuette June 18, 1940 2,280,722 Schneider Apr. 21, 1942 2,320,225 Ericks May 25, 1943 2,381,121 Ericks Aug, 7, 1945 2,406,867 Tomlinson Sept. 3, 1946 2,469,493 Burker May lo, 1949 

1. THE METHOD OF PRODUCING CONDENSATION PRODUCTS WHICH COMPRISES CONTINUOUSLY INTRODUCING-AN UNSUBSTITUTED ALKYLENE OXIDE WHICH BOILS BELOW 200* C. INTO A REACTION ZONE AT SUCH A RATE THAT THE PRESSURE IN SAID ZONE IS MAINTAINED SUBSTANTIALLY CONSTANT, SPRAYING IN A FINELY DIVIDED LIQUID FORM INTO SAID ZONE AN ORGANIC COMPOUND CONTAINING AT LEAST ONE REACTIVE HYDROGEN ATOM AND AT LEAST SIX CARBON ATOMS WHICH THEN REACTS WITH A PORTION OF SAID ALKYLENE OXIDE, COOLING AND CONTINUOUSLY RECYCLING AND SPRAYING THE RESULTING PRODUCTS INTO SAID ZONE FOR FURTHER REACTION UNTIL A PREDETERMINED NUMBER OF ALKYLENE OXIDE GROUPS HAVE BEEN INTRODUCED INTO SAID COMPOUND, SAID ORGANIC COMPOUND BEING SELECTED FROM THE GROUP CONSISTING OF HYDROXYL, CARBOXYL, AMINO AND MERCAPTO COMPOUNDS, AND SAID COOLING BEING SUF- 